atmosphere

Article
Atmospheric Mercury Deposition in Macedonia from
2002 to 2015 Determined Using the Moss
Biomonitoring Technique
Trajče Stafilov 1, *, Lambe Barandovski 2, *, Robert Šajn 3 and Katerina Bačeva Andonovska 4
1 Institute of Chemistry, Faculty of Natural Sciences and Mathematics, Ss. Cyril and Methodius University,
POB 162, 1000 Skopje, Macedonia
2 Institute of Physics, Faculty of Natural Sciences and Mathematics, Ss. Cyril and Methodius University,
POB 162, 1000 Skopje, Macedonia
3 Geological Survey of Slovenia, Dimičeva 14, 1000 Ljubljana, Slovenia; Robert.Sajn@GEO-ZS.SI
4 Research Center for Environment and Materials, Academy of Sciences and Arts of the Republic of North
Macedonia—MANU, Krste Misirkov 2, 1000 Skopje, Macedonia; kbaceva@manu.edu.mk
* Correspondence: trajcest@pmf.ukim.mk (T.S.); lambe@pmf.ukim.mk (L.B.);
Tel.: +38970350756 (T.S.); +38970607921 (L.B.)




Received: 2 November 2020; Accepted: 18 December 2020; Published: 21 December 2020


Abstract: The moss biomonitoring technique was used in 2002, 2005, 2010 and 2015 in a potentially
toxic elements study (PTEs) in Macedonia. For that purpose, more than 70 moss samples from
two dominant species (Hypnum cupressiforme and Homalothecium lutescens) were collected during
the summers of the mentioned years. Total digestion of the samples was done using a microwave
digestion system, whilst mercury was analyzed by cold vapour atomic absorption spectrometry
(CV–AAS). The content of mercury ranged from 0.018 mg/kg to 0.26 mg/kg in 2002, from 0.010 mg/kg
to 0.42 mg/kg in 2005, from 0.010 mg/kg to 0.60 mg/kg in 2010 and from 0.020 mg/kg to 0.25 mg/kg in
2015. Analysis of the median values shows the increase of the content in the period 2002–2010 and a
slight reduction of the air pollution with Hg in the period 2010–2015. Mercury distribution maps show
that sites with increased concentrations of mercury in moss are likely impacted by anthropogenic
pollution. The results were compared to similar studies done during the same years in neighboring
countries and in Norway—which is a pristine area and serves as a reference, and it was concluded
that mercury air pollution in Macedonia is significant primarily in industrialized regions.

Keywords: air pollution; moss biomonitoring; potentially toxic elements; mercury; CV–AAS;
Macedonia

1. Introduction
Air pollutants are considered all chemical compounds or elements released into the atmosphere
that pose health hazards to ecosystems and humans [1]. The majority of potentially toxic elements
(PTEs) originate mainly from anthropogenic sources [2–4]. Natural sources of these elements include
volcanoes, forest fires, biological decomposition processes and oceans [4]. The largest anthropogenic
sources of PTEs in the atmosphere are the combustion of fossil and biofuels, traffic and emissions from
industrial processes [5,6].
Due to the specific features and the effects on human health, the discharge of mercury in the
environment has been identified as a global problem [7]. Even the mercury is naturally occurring in
the Earth’s crust, the atmospheric emission is mostly in an elemental mercury vapour form. Mercury
enters the environment through volcanic eruptions and erosion of natural mercury–containing deposits,
but also from forest fires and uncontrolled coal bed fires [7]. Anthropogenic sources of Hg are

Atmosphere 2020, 11, 1379; doi:10.3390/atmos11121379 www.mdpi.com/journal/atmosphere

Atmosphere 2020, 11, 1379 2 of 10

mostly connected with extraction refining and use of fossil fuels, metal production (Cu, Zn, Pb, etc.),
production of inorganic materials (cement, paper production), recycling processes, chlorine–alkaline
processes, etc. [7] High concentrations of mercury in human organism impact the central nervous
system, especially the sensory, auditory and visual, parts of the brain that can affect coordination,
lower immunity, heart attack risk, nervous system damage, and impair reproduction [8,9]. Therefore,
timely and reliable identification of mercury discharge and presence in the environment is crucial.
Estimation of atmospheric heavy metal deposition using carpet–forming moss was done for the
first time in the 1960s by Rühling and Tyler [10]. The moss analysis technique provides an alternative,
time–integrated measure of the spatial patterns of PTEs deposition from the atmosphere to terrestrial
ecosystems. The technique avoids the need for deploying large numbers of deposition collectors with
an associated long–term programme of routine sample collection. Since 1990, the European moss
survey has been repeated at five–yearly intervals [5,6,11,12] and the latest survey was conducted in
2015 with more than 35 participating countries [13]. The European moss survey gives data on the
contents of ten potentially toxic metals (As, Cd, Cr, Cu, Fe, Hg, Ni, Pb, V, Zn) as well as the content of
nitrogen [13–16].
The first study of mercury air pollution on the whole territory of Macedonia, using moss species
as biomonitors, was undertaken in 2002, and the study was repeated in 2005, 2010, and 2015 within the
European moss survey [17–23]. Pollution of soil samples with Hg, obtained in the vicinity of town
Veles, due to work of the lead and zinc metallurgical plant situated near the town, was studied by
Stafilov et al. [24,25] showing the increase of the content of Hg in topsoil over the European Hg average
by a factor of 3.2. Analysis of the 174 soil samples collected in Kavadarci, an area in the south of
the country [26,27] showed both lithogenic and anthropogenic influence of mercury in the collected
samples. In some area along the river Vardar and the city of Kavadarci, the content of Hg was up
to 3.8 mg/kg. Increased content of Hg was also found in soil samples in the vicinity of the “Allchar”
As–Sb–Tl mine, located to the south of the city of Kavadarci [28]. This mine is lithogenic in origin
but contributes to localized air pollution and it has been shown to influence the communities in this
geographic area presenting natural phenomena.
The aims of this work are to investigate and present the temporal trends of the content of Hg in
moss samples from the results of the surveys performed in the 2002–2015 period, to determine the
places most affected by Hg pollution, and to try to connect the pollution with known anthropogenic
activities in the regions, to distinguish natural from anthropogenic sources, to identify the deposition
patterns and to compare results with previous studies in the neighboring countries and pristine areas.

2. Materials and Methods

2.1. Study Area

The Republic of Macedonia is a landlocked country situated in the central part of the Balkan
Peninsula. Macedonia is bordering Serbia and Kosovo to the north, Bulgaria to the east, Albania to
the west, and Greece to the south (Figure 1). A detailed description of the country (location, climate,
and demographics) can be found elsewhere [17–23,29,30]. The location of main industrial activities
and their input of different PTEs, has been also previously reported in several studies [31–46].

2.2. Sampling Sample Preparation and Instrumentation

In 2002, 2005, 2010 and 2015 moss samples from two moss species were collected on the entire
territory of Macedonia [17–23]. In total, 72 moss samples were collected in each of the sampling
campaigns (Figure 2). Collected moss samples were from the two most abundant moss species
(Hypnum cupressiforme and Homalothecium lutescens). In locations where the two–moss species were
collected, the interspecies comparison showed no differences within error estimates. The sampling
procedure followed the principles of European moss surveys [12,47–49]. The moss samples were
 Atmosphere 2020, 11, 1379 3 of 10
Atmosphere 2020, 11, x FOR PEER REVIEW 3 of 10
Atmosphere 2020, 11, x FOR PEER REVIEW 3 of 10

previously
previously digested
previously
digested byby
digested microwave
microwave
by microwave digestion
digestion system
digestion
systemsystematoat
at 180 180 oC ◦with nitric acid and then mercury was
C 180
with Cnitric
withacid
nitric acid
and andmercury
then then mercury
was was
determined
determinedby cold
by vapor
cold atomic
vapor absorption
atomic spectrometry
absorption spectrometry (CV–AAS)
(CV–AAS)
determined by cold vapor atomic absorption spectrometry (CV–AAS) [50]. [50].
[50].

Figure 1. Map of the Republic of Macedonia.

Figure Figure of Map
1. Map 1. of the
the RepublicRepublic of Macedonia.
of Macedonia.

Figure 2. Location of sampling

2. Location points.
of sampling
Figure Figure
2. Location of sampling points. points.
Atmosphere 2020, 11, 1379 4 of 10

2.3. Quality Control

The quality control of Hg determination was ensured by standard reference materials M2 and M3,
which are prepared for the European Moss Survey [50,51] as well as the standard addition method.

2.4. Statistical Methods

Statistical analysis of the obtained data from the studies were made using the statistical software
Statistica 13 (StatSoft, Inc., Tulsa, OK, USA) [52,53]. The common universal kriging with linear
variogram interpolation method was applied to construct the maps of mercury areal distribution [54].
The basic grid cell size for interpolation was 1 × 1 km. For class limits the percentile values of
distribution of all interpolated values (2002/2005/2010/2015) were chosen. Seven classes of the following
percentile values were selected: 0–10, 10–25, 25–40, 40–60, 60–75, 75–90 and 90–100. In addition,
an analysis of variance (ANOVA) was performed which showed significant differences between the
four sampling seasons.

3. Results and Discussion

Results of the descriptive statistics of mercury content in the moss samples collected in 2002, 2005,
2010, and 2015 are given in Table 1. In Table 2, the obtained results were compared with the results
of the content off Hg in moss samples obtained from similar studies in the neighbouring countries,
as well as Norway which is considered a pristine area. The maps of the spatial distribution of Hg in
moss samples collected in 2002, 2005, 2010, and 2015 to observe the trends of pollution in Macedonia
during this period are given in Figures 3 and 4.

Table 1. Descriptive statistics of measurement according to sampling campaign, (in mg/kg).

N Xa Md Min Max P10 P90 S CV A E

2002 72 0.069 0.056 0.018 0.26 0.034 0.114 0.040 60 2.03 7.08
2005 72 0.080 0.068 0.010 0.42 0.012 0.14 0.072 89 2.40 7.69
2010 72 0.110 0.093 0.010 0.60 0.05 0.16 0.094 84 3.57 14.2
2015 72 0.087 0.084 0.020 0.25 0.020 0.15 0.050 58 0.67 0.75
N—number of samples, Xa —arithmetic mean, Md—median, Min—minimum, Max—maximum, P10 —10 percentile,
P90 —90 percentile, S—standard deviation, CV—coefficient of variation, A—asymmetry, E—distribution.

Table 2. The median values and ranges for the content of Hg obtained for Macedonia, neighbouring
countries, and Norway.

No. of Samples Median (mg/kg) Range (mg/kg)

Macedonia, 2002 72 0.056 0.018–0.26
Serbia, 2000 [55] 92 0.386 0.01–2.69
Norway, 2000 [11] 464 0.052 0.022–0.208
Macedonia, 2005 72 0.068 0.010–0.42
Croatia, 2006 [50] 94 0.064 0.007–0.301
Slovenia, 2005 [48] 57 0.095 0.050–0.175
Norway, 2005 [48] 100 0.046 0.026–0.166
Macedonia, 2010 72 0.093 0.010–0.60
Croatia, 2010 [56] 121 0.043 0.010–0.145
Slovenia, 2010 [6] 63 0.056 0.030–0.16
Albania 2010 [6] 59 0.130 0.031–2.23
Kosovo 2010 [6] 25 0.033 0.009–0.35
Norway, 2010 [6] 463 0.060 <0.024–0.34
Macedonia, 2015 72 0.084 0.020–0.25
Albania, 2015 [57] 55 0.049 0.006–0.21
Norway, 2015 [58] 229 0.050 0.005–0.53
 Albania 2010 [6] 59 0.130 0.031–2.23
Kosovo 2010 [6] 25 0.033 0.009–0.35
Norway, 2010 [6] 463 0.060 <0.024–0.34
Macedonia, 2015 72 0.084 0.020–0.25
Albania, 2015 [57] 55 0.049 0.006–0.21
Atmosphere 2020, 11, 1379 5 of 10
Norway, 2015 [58] 229 0.050 0.005–0.53

Atmosphere 2020, 11, x FOR PEER REVIEW 7 of 10

sources of mercury releases in the country and estimates or quantifies the releases which are
Figure
consistent with theFigure Box plots
plots
3.obtained
results3. Box of these
from
of Hg according
Hg according to the
the
studies using
to yearbiomonitoring.
moss
year of sampling.
of sampling.

The mean value of mercury content in the moss samples increased in the period 2002–2010,
while the value decreased for the samples collected in 2015 (Table 2, Figure 3). The coefficients of
variation (CV%) are very high, with high values of asymmetry and distribution with a large range
of variation of the positively skewed concentration data indicating the influence of different natural
and anthropogenic factors. In addition, an analysis of variance (ANOVA) was performed which
showed significant differences between the four sampling seasons (F = 5.43 / p = 0.0012), which
means that moss biomonitoring every 5 years is appropriate.
From the results of median values and the ranges of the content of Hg in Macedonia and those
obtained in some neighbouring countries and Norway (Table 2), it can be seen that the median
value obtained in 2002 (0.056 mg/kg) is slightly higher than the median value obtained from the
survey in the same year in Norway [58] (which is usually considered as a pristine area [11]) (0.052

FigureFigure 4. Distribution
4. Distribution of Hg
of Hg ininmoss
mosssamples
samples collected
collectedin in
2002, 2005,
2002, 2010 2010
2005, and 2015.
and 2015.
4. Conclusions
The mean value of mercury content in the moss samples increased in the period 2002–2010,
The content
while the value of mercury
decreased for thewas determined
samples in moss
collected in samples collected
2015 (Table in 2002,3).
2, Figure 2005,
The2010, and
coefficients of
2015 all over the territory of Macedonia by using CV–AAS. ANOVA analysis of the results showed
significant difference between the results obtained in the four sampling seasons. Although
distribution maps show some differences and a discrepancy, the largest anthropogenic impact of air
pollution with mercury was found near the abandoned lead–zinc smelter in the town of Veles, lead
and zinc mines Sasa, Zletovo and Toranica – in the north–eastern part of the country, ferronickel
smelter at the vicinity of the town of Kavadarci, and the copper mine and flotation near the town of
Atmosphere 2020, 11, 1379 6 of 10

variation (CV%) are very high, with high values of asymmetry and distribution with a large range of
variation of the positively skewed concentration data indicating the influence of different natural and
anthropogenic factors. In addition, an analysis of variance (ANOVA) was performed which showed
significant differences between the four sampling seasons (F = 5.43/p = 0.0012), which means that moss
biomonitoring every 5 years is appropriate.
From the results of median values and the ranges of the content of Hg in Macedonia and those
obtained in some neighbouring countries and Norway (Table 2), it can be seen that the median value
obtained in 2002 (0.056 mg/kg) is slightly higher than the median value obtained from the survey in
the same year in Norway [58] (which is usually considered as a pristine area [11]) (0.052 mg/kg) and
9.9 times lower than those obtained for Serbia [55]. The median value obtained for the 2005 study
is comparable with the median value obtained in the similar study done in Croatia [56], lower than
the median value for Slovenia [48] and 1, 5 times higher in comparison with the median value for
Norway [48]. The obtained median value for 2010 is higher than the values obtained in the neighbouring
countries except in the case of Albania [15], which is the case for data for 2015 as well. It should be also
emphasized that the maximal value for the content of Hg in moss samples from Macedonia in 2002,
2005, and 2010 is higher than the maximal content of Hg in moss samples from Norway, while in 2015
is twice smaller.
Distribution maps based on the content of Hg in moss samples collected in 2002, 2005, 2010 and 2015
(Figure 4) show some differences and a discrepancy, i.e., variation with time as well as geographically,
but it can be noticed that an increased Hg content is visible in the same regions for the whole period
of the research. In 2002, the higher Hg content in the moss samples can be seen along the valley of
the river Vardar, which extends from the cities of Skopje to Veles and continues southeast toward the
border with Greece. It should be also mentioned that in 2002 pollution with Hg is connected with
the activities of the lead and zinc smelter plant in the town of Veles [25] which had operated until
2003, as well with the work of the steelwork in Skopje [17,45]. Higher content of Hg in the mosses
collected in 2002 sampling campaign was observed on the north–eastern part of the country (in the
vicinity of the town of Kočani) where three Pb–Zn mines and flotation plants (Sasa, Toranica, Zletovo)
are located [39].
In 2005 the enrichment of Hg was connected with the operation of the steelwork in Skopje [18] as
well as the pollution by the lead and zinc smelter plant in Veles despite its closure in 2003. In contrast
with the moss survey in 2002, enrichment with Hg in 2005 is also observed in the areas of Bitola in the
south–western part of the country and in the west–central part of the country near the town of Kičevo,
where two thermoelectric power plants using not pre–treated i.e. pre–washed prior combustion
coal–lignite for energy production are located. Higher content of Hg in the mosses is also noticed
in the eastern part of the country, near the town of Radoviš where copper mine and flotation were
reactivated in this period.
With the reactivation of Pb–Zn mines (Toranica, Zletovo, and Sasa), in 2010 the enrichment of the
content of Hg was observed in the eastern part of Macedonia. In the period of 2001/02 until 2006/07
these mines were not active, but in 2006 (Sasa) and 2007 (Toranica, Zletovo) were reactivated. In the
mining area, millions of tons of flotation tailings are deposited on the ground, and can easily be
dispersed into the biosphere by wind [39–41]. Furthermore, the enrichment in 2010 is also observed
in the area of the steelwork in Skopje, near Bitola, Kičevo, but also near Kavadarci which is related
to reactivation and the increasing of the production capacity of the ferro–nickel smelter in 2004 [19].
Higher content of Hg in the mosses collected near the western border of the country can be explained
by the transboundary transport from Albania where the content of Hg in the mosses in this period was
substantially higher than the samples collected in Macedonia [57].
Although the median value of Hg content in the mosses in Macedonia in 2015 is lower than the
one in 2010, the high values are observed in the same areas as in the previous years.
High enrichment of the moss samples collected near the capital of Skopje, is partially connected
with the presence of mercury–contaminated sites at the former “Organic Chemical Industry in Skopje
Atmosphere 2020, 11, 1379 7 of 10

–OHIS” chlor–alkali plant situated in the town (operational from 1964 until 1995). The plant was
based on mercury cell electrolysis and during the whole operational period, sodium hydroxide and
hydrochloric acid were produced. It is assumed that part of the waste arising from the chlorine
production containing mercury was dumped onto the mixed waste dump within the plant surrounding
and that 400 tons of mercury were lost in the environment [59].
The results from this study and from previous work [24–27], in which the content of Hg in
various environmental samples (soil, water, sediments) were determined, has been used to prepare the
Minamata Initial Assessment in the Republic of Macedonia and the National inventory on mercury
releases developed in 2017 [59]. The reference base year is 2013 and data for this year have been used
in the inventory when available. The National mercury inventory identified most of the sources of
mercury releases in the country and estimates or quantifies the releases which are consistent with the
results obtained from these studies using moss biomonitoring.

4. Conclusions
The content of mercury was determined in moss samples collected in 2002, 2005, 2010, and 2015 all
over the territory of Macedonia by using CV–AAS. ANOVA analysis of the results showed significant
difference between the results obtained in the four sampling seasons. Although distribution maps show
some differences and a discrepancy, the largest anthropogenic impact of air pollution with mercury was
found near the abandoned lead–zinc smelter in the town of Veles, lead and zinc mines Sasa, Zletovo and
Toranica – in the north–eastern part of the country, ferronickel smelter at the vicinity of the town of
Kavadarci, and the copper mine and flotation near the town of Radoviš. The high content of mercury
in the moss samples was also observed near the two thermoelectric power plants located in the vicinity
of the towns of Bitola and Kičevo. Evidence of transboundary transport from Albania was observed in
the western part of the country in samples collected in 2010 and 2015. Elevated values of Hg content
in the moss samples collected near Skopje can be explained with the work of the former chlor–alkali
plant “OHIS” and the inappropriate deposition of mercury–contaminated waste in the vicinity of this
plant. This work is essential for modeling the mercury pollution in Macedonia, as well as monitoring
the future trends aiming to preserve the quality of the ecosystems from deteriorating.

Author Contributions: Conceptualization, L.B. and T.S.; methodology, T.S.; software, R.Š.; investigation, T.S.; L.B.
and K.B.A.; data curation, R.Š.; writing—original draft preparation, L.B.; writing—review and editing, L.B. and
T.S.; visualization, R.Š. All authors have read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Moriarty, F. Ecotoxicology—The Study of Pollutants in Ecosystems, 3rd ed.; Academic Press: San Diego, CA,
USA, 1999.
2. Whelpdale, D.M.; Summers, P.W.; Sanhueza, E. A global overview of atmospheric acid deposition fluxes.
Environ. Monit. Assess. 1998, 48, 217–247. [CrossRef]
3. Pacyna, J.M.; Pacyna, E.G. An assessment of global and regional emissions of trace metals to the atmosphere
from anthropogenic sources worldwide. Environ. Rev. 2001, 9, 269–298. [CrossRef]
4. Nriagu, J.O. A global assessment of natural sources of atmospheric trace metals. Nature 1999, 338, 47–49. [CrossRef]
5. Harmens, H.; Norris, D.A.; Steinnes, E.; Kubin, E.; Piispanen, J.; Alber, R.; Aleksiayenak, Y.; Blum, O.;
Coşkun, M.; Dam, M.; et al. Mosses as biomonitors of atmospheric heavy metal deposition: Spatial and
temporal trends in Europe. Environ. Pollut. 2010, 158, 3144–3156. [CrossRef]
6. Harmens, H.; Norris, D.A.; Sharps, K.; Mills, G.; Alber, R.; Aleksiayenak, Y.; Blum, O.; Cucu–Man, S.M.;
Dam, M.; De Temmerman, L.; et al. Heavy metal and nitrogen concentrations in mosses are declining across
Europe whilst some “hotspots” remain in 2010. Environ. Pollut. 2015, 200, 93–104. [CrossRef]
Atmosphere 2020, 11, 1379 8 of 10

7. Pirrone, N.; Cinnirella, S.; Feng, X.; Finkelman, R.B.; Friedli, H.R.; Leaner, J.; Mason, R.; Mukherjee, A.B.;
Stracher, G.B.; Streets, D.G.; et al. Global mercury emissions to the atmosphere from anthropogenic and
natural sources. Atmos. Chem. Phys. 2010, 10, 5951–5964. [CrossRef]
8. Clarkson, T.W. The toxicology of mercury. Crit. Rev. Toxicol. 1997, 34, 369–403. [CrossRef]
9. Tchounwou, P.B.; Ayensu, W.K.; Ninashvili, N.; Sutto, D. Environmental exposure to mercury and its
toxicopathologic implications for public health. Environ. Toxic. 2003, 18, 149–175. [CrossRef]
10. Rühling, Å.; Tyler, G. An ecological approach to the lead problem. Bot. Not. 1968, 122, 248–342.
11. Harmens, H.; Buse, A.; Büker, P.; Norris, D.; Mills, G.; Williams, B. Heavy metal concentrations in European
mosses: 2000/2001 survey. J. Atmos. Chem. 2004, 49, 425–436. [CrossRef]
12. Rühling, Å.; Steinnes, E. Atmospheric Heavy Metal Deposition in Europe 1995–1996. NORD 1998:15;
Nordic Council of Ministers: Copenhagen, Denmark, 1998.
13. Frontasyeva, M.; Harmens, H.; Uzhinskiy, A.; Chaligava, O.; Aničić Urošević, M.; Vergel, K.; Tepanosyan, G.;
Steinnes, E.; Aleksiayenak, Y.; Tabors, G.; et al. Mosses as Biomonitors of Air Pollution: 2015/2016 Survey on Heavy
Metals, Nitrogen and POPs in Europe and Beyond; Joint Institute for Nuclear Research JINR: Dubna, Russia, 2020.
14. Harmens, H.; Norris, D.A.; Koerber, G.R.; Buse, A.; Steinnes, E.; Rühling, Å. Temporal trends in the
concentration of arsenic, chromium, copper, iron, nickel, vanadium and zinc in mosses across Europe
between 1990 and 2000. Atmos. Environ. 2007, 41, 6673–6687. [CrossRef]
15. Harmens, H.; Norris, D.A.; Koerber, G.R.; Buse, A.; Steinnes, E.; Rühling, Å. Temporal trends (1990x2000)
in the concentration of cadmium, lead and mercury in mosses across Europe. Environ. Poll. 2008, 151,
368–376. [CrossRef]
16. Nickel, S.; Schröder, W.; Schmalfuss, R.; Saathoff, M.; Harmens, H.; Mills, G.; Frontasyeva, M.V.;
Barandovski, L.; Blum, O.; Carballeira, A.; et al. Modelling spatial patterns of correlations between
concentrations of heavy metals in mosses and atmospheric deposition in 2010 across Europe. Environ. Sci.
Eur. 2018, 30, 53. [CrossRef]
17. Barandovski, L.; Cekova, M.; Frontasyeva, M.V.; Pavlov, S.S.; Stafilov, T.; Steinnes, E.; Urumov, V.
Atmospheric deposition of trace element pollutants in Macedonia studied by the moss biomonitoring
technique. Environ. Monit. Assess. 2008, 138, 107–118. [CrossRef]
18. Barandovski, L.; Frontasyeva, M.V.; Stafilov, T.; Šajn, R.; Pavlov, S.; Enimiteva, V. Trends of atmospheric
deposition of trace elements in Macedonia by the moss biomonitoring technique. J. Environ. Sci. Health A
2012, 47, 2000–2015. [CrossRef]
19. Barandovski, L.; Stafilov, T.; Šajn, R.; Frontasyeva, M.V.; Bačeva, K. Air pollution study in Macedonia using a
moss biomonitoring technique, ICP–AES, and AAS. Maced. J. Chem. Chem. Eng. 2013, 32, 89–107. [CrossRef]
20. Barandovski, L.; Frontasyeva, M.V.; Stafilov, T.; Šajn, R.; Ostrovnaya, T.M. Multi–element atmospheric
deposition in Macedonia studied by the moss biomonitoring technique. Environ. Sci. Pollut. Res. 2015, 22,
16077–16097. [CrossRef] [PubMed]
21. Stafilov, T.; Šajn, R.; Barandovski, L.; Bačeva, K.A.; Malinovska, S. Moss biomonitoring of atmospheric
deposition study of minor and trace elements in Macedonia. Air Qual. Atmos. Health 2018, 11,
137–152. [CrossRef]
22. Stafilov, T.; Špirić, Z.; Glad, M.; Barandovski, L.; Andonovska, K.B.; Šajn, R.; Antonić, O. Study of nitrogen
pollution in the Republic of North Macedonia by moss biomonitoring and Kjeldahl method. J. Environ. Sci.
Health A 2020, 55, 759–764. [CrossRef] [PubMed]
23. Barandovski, L.; Stafilov, T.; Šajn, R.; Frontasyeva, M.; Bačeva Andonovska, K. Atmospheric heavy metal
deposition in North Macedonia from 2002 to 2010 studied by the moss biomonitoring technique. Atmosphere
2020, 11, 929. [CrossRef]
24. Stafilov, T.; Šajn, R.; Pančevski, Z.; Boev, B.; Frontasyeva, M.V.; Strelkova, L.P. Geochemical Atlas of Veles and the
Environs; Faculty of Natural Sciences and Mathematics: Skopje, Macedonia, 2008.
25. Stafilov, T.; Šajn, R.; Pančevski, Z.; Boev, B.; Frontasyeva, M.V.; Strelkova, L.P. Heavy metal contamination
of surface soils around a lead and zinc smelter in the Republic of Macedonia. J. Hazard. Mater. 2010, 175,
896–914. [CrossRef]
26. Stafilov, T.; Šajn, R.; Boev, B.; Cvetković, J.; Mukaetov, D.; Andreevski, M. Geochemical Atlas of Kavadarci and
the Environs; Faculty of Natural Sciences and Mathematics: Skopje, Macedonia, 2008.
Atmosphere 2020, 11, 1379 9 of 10

27. Stafilov, T.; Šajn, R.; Boev, B.; Cvetković, J.; Mukaetov, D.; Andreevski, M.; Lepitkova, S. Distribution of some
elements in surface soil over the Kavadarci Region, Republic of Macedonia. Environ. Earth Sci. 2010, 61,
1515–1530. [CrossRef]
28. Bačeva, K.; Stafilov, T.; Šajn, R.; Tănăselia, C.; Makreski, P. Distribution of chemical elements in soils and
stream sediments in the area of abandoned Sb–As–Tl Allchar mine, Republic of Macedonia. Environ. Res.
2014, 133, 77–89. [CrossRef] [PubMed]
29. State Statistical Office of the Republic of Macedonia. Environmental Statistics. 2019. Available online:
http://www.stat.gov.mk/Publikacii/ZivotnaSredina2019.pdf (accessed on 15 November 2020).
30. Lazarevski, A. Climate in Macedonia; Kultura: Skopje, Macedonia, 1993. (In Macedonian)
31. Balabanova, B.; Stafilov, T.; Bačeva, K.; Šajn, R. Biomonitoring of atmospheric pollution with heavy metals in
the copper mine vicinity located near Radoviš, Republic of Macedonia. J. Environ. Sci. Health A 2010, 45,
1504–1518. [CrossRef]
32. Balabanova, B.; Stafilov, T.; Šajn, R.; Bačeva, K. Distribution of chemical elements in attic dust as reflection of
lithology and anthropogenic influence in the vicinity of copper mine and flotation. Arch. Environ. Contam.
Toxicol. 2011, 6, 173–184. [CrossRef] [PubMed]
33. Bačeva, K.; Stafilov, T.; Šajn, R.; Tănăselia, C.; Ilić Popov, S. Distribution of chemical elements in attic dust in
the vicinity of ferronickel smelter plant. Fresenius Environ. Bull. 2011, 20, 2306–2314.
34. Bačeva, K.; Stafilov, T.; Šajn, R.; Tănăselia, C. Moss biomonitoring of air pollution with heavy metals in the
vicinity of a ferronickel smelter plant. J. Environ. Sci. Health A 2012, 47, 645–656. [CrossRef]
35. Bačeva, K.; Stafilov, T.; Šajn, R.; Tănăselia, C. Air dispersion of heavy metals in vicinity of the As–Sb–Tl
abounded mine and responsiveness of moss as a biomonitoring media in small scale investigations.
Environ. Sci. Pollut. Res. 2013, 20, 8763–8779. [CrossRef]
36. Stafilov, T. Environmental pollution with heavy metals in the Republic of Macedonia. Contrib. Sect. Nat.
Math. Biotechnol. Sci. MASA 2014, 35, 81–119. [CrossRef]
37. Balabanova, B.; Stafilov, T.; Šajn, R.; Bačeva, K. Comparison of response of moss, lichens and attic
dust to geology and atmospheric pollution from copper mine. Int. J. Environ. Sci. Technol. 2014, 11,
517–528. [CrossRef]
38. Angelovska, S.; Stafilov, T.; Šajn, R.; Bačeva, K.; Balabanova, B. Moss biomonitoring of air pollution with
heavy metals in the vicinity of Pb–Zn mine “Toranica” near the town of Kriva Palanka. Modern Chem. Appl.
2014, 2, 1–6.
39. Balabanova, B.; Stafilov, T.; Šajn, R.; Tănăselia, C. Multivariate extraction of dominant geochemical markers for
69 elements deposition in Bregalnica River Basin, Republic of Macedonia (moss biomonitoring). Environ. Sci.
Poll. Res. 2016, 23, 22852–22870. [CrossRef] [PubMed]
40. Balabanova, B.; Stafilov, T.; Šajn, R.; Bačeva Andonovska, K. Quantitative assessment of metal elements using
moss species as biomonitors in downwind area of lead-zinc mine. J. Environ. Sci. Health A 2017, 52, 290–301.
41. Stafilov, T.; Šajn, R. Geochemical Atlas of the Republic of Macedonia; Faculty of Natural Sciences and Mathematics,
Sc. Cyril and Methodius University: Skopje, Macedonia, 2016.
42. Stafilov, T.; Šajn, R.; Arapčeska, M.; Kungulovski, I.; Alijagić, J. Geochemical properties of topsoil around the
coal mine and thermoelectric power plant. J. Environ. Sci. Health A 2018, 53, 793–808.
43. Stafilov, T.; Šajn, R.; Sulejmani, F.; Bačeva, K. Geochemical properties of topsoil around the open coal mine
and Oslomej thermoelectric power plant R.; Macedonia. Geol. Croat. 2014, 67, 33–44. [CrossRef]
44. Balabanova, B.; Stafilov, T.; Šajn, R. Enchasing anthropogenic element trackers for evidence of long-term
atmospheric depositions in mine environ. J. Environ. Sci. Health A 2019, 54, 988–998.
45. Stafilov, T.; Šajn, R.; Ahmeti, L. Geochemical characteristics of soil of the city of Skopje, Republic of Macedonia.
J. Environ. Sci. Health A 2019, 54, 972–987.
46. Stafilov, T.; Šajn, R. Spatial distribution and pollution assessment of heavy metals in soil from the Republic of
North Macedonia. J. Environ. Sci. Health A 2019, 54, 1457–1474.
47. Harmens, H.; Mills, G.; Hayes, F.; Williams, P.; Soja, G.; Riss, A.; Zechmeister, H.G.; Temmerman, L.D.;
Yurukova, L.; Stamenov, J.; et al. Air pollution and Vegetation, ICP Vegetation Annual Report 2003/2004;
ICP Vegetation Coordination Centre: Bangor, UK, 2004.
48. Harmens, H.; Mills, G.; Hayes, F.; Williams, P.; Temmerman, L.D.; Soja, G.; Stabentheiner, E.; Riss, A.;
Zechmeister, H.G.; Zhuk, I.; et al. Air Pollution and Vegetation ICP Vegetation Annual Report 2004/2005;
ICP Vegetation Coordination Centre: Bangor, UK, 2005.
Atmosphere 2020, 11, 1379 10 of 10

49. Harmens, H.; Mills, G.; Hayes, F.; Norris, D.; Lazo, P.; Soja, G.; Zechmeister, H.; Aleksiayenek, Y.;
Temmerman, L.D.; Vandermeiren, K.; et al. Air Pollution and Vegetation ICP Vegetation Annual Report
2011/2012; ICP Vegetation Coordination Centre: Bangor, UK, 2012.
50. Špirić, Z.; Vučković, I.; Stafilov, T.; Kušan, V.; Bačeva, K. Biomonitoring of air pollution with mercury in
Croatia by using moss species and CV–AAS. Environ. Monit. Assess. 2014, 186, 4357–4366. [CrossRef]
51. Steinnes, E.; Rühling, Å.; Lippo, H.; Mäkinen, A. Reference material for large-scale metal deposition surveys.
Accredit. Qual. Assur. 1997, 2, 243–249.
52. Snedecor, G.W.; Cochran, W.G. Statistical Methods; The Iowa State University Press: Ames, IA, USA, 1967.
53. Hollander, M.; Wolfe, D.A. Nonparametric Statistical Methods, 2nd ed.; Wiley: New York, NY, USA, 1999.
54. Davis, J.C. Statistic and Data Analysis in Geology; Willey: New York, NY, USA, 1986; p. 646.
55. Frontasyeva, M.V.; Galinskaya, T.Y.; Krmar, M.; Matavulj, M.; Pavlov, S.S.; Radnović, D.; Steinnes, E.
Atmospheric deposition of heavy metals in northern Serbia and Bosnia-Herzegovina studied by moss
biomonitoring, neutron activation analysis and GIS technology. J. Radioanal. Nucl. Chem. 2004, 259,
141–147. [CrossRef]
56. Špirić, Z.; Frontasyeva, M.; Steinnes, E.; Stafilov, T. Multi–element atmospheric deposition study in Croatia.
Int. J. Environ. Anal. Chem. 2012, 92, 1200–1214. [CrossRef]
57. Lazo, P.; Stafilov, T.; Qarri, F.; Allajbeu, S.; Bekteshi, L.; Frontasyeva, M.; Harmens, H. Spatial distribution
and temporal trend of airborne trace metal deposition in Albania studied by moss biomonitoring. Ecol. Indic.
2019, 101, 1007–1017. [CrossRef]
58. Steinnes, E.; Uggerud, H.T.; Pfaffhuber, K.A.; Berg, T. Atmospheric Deposition of Heavy Metals in Norway—National
Moss Survey 2015. M–595; Norwegian Institute for Air Research: Trondheim, Norway, 2015.
59. Stafilov, T.; Mickovski, A.; Mihajlov, M. National Inventory of Mercury Releases in the Republic of Macedonia;
Ministry of Environment and Physical Planning: Skopje, Macedonia, 2017.

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